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POTASH  SHALES 


BY 


WILLIAM  A.  WILLIS 


THESIS 


FOR  THE 


DEGREE  OF  BACHELOR  OF  SCIENCE 

IN 


CHEMICAL  ENGINEERING 


COLLEGE  OF  LIBERAL  ARTS  AND  SCIENCES 


UNIVERSITY  OF  ILLINOIS 


1922 


Digitized  by  the  Internet  Archive 

in  2015 


https://archive.org/details/postashshalesOOwebs 


UNIVERSITY  OF  ILLINOIS 


mY__27.^__i92.2__ 


THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 

-W-ILL-IAM  

ENTITLED POTASS -SHA.LES 


IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 
DEGREE  OF  BAQHELilB^.0F_5_QLEN0E 


XS_QlimaAL_EIC3XIIEEBXHG 


Instructor  in  Charge 


Approved  : 


ACTING  HEAD  OF  DEPARTMENT  OF  _OHEMISTRY. 


k jT. 


Table  of  Contents 


Page, 

Acknowledgement*  1 

I.  Introduction,  2 

II.  History,  3 

III.  Experimental,  5 

IV.  Conclusion.  d 

Bibliography,  11 


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2 


Introduction. 

In  various  parts  of  Illinois  there  are  peaty  soils 
which  are  all  more  or  less  deficient  in  potassium  as  a 
source  of  plant  nutrition.  Also,  there  are  shale  deposits 
in  this  state  that  yield  a quantity  of  potash  sufficient 
to  maJ^e  it  valuable  as  a fertilizer,  if  this  potash  is  in 
a form  which  would  render  it  available  for  plant  use* 

The  work  done  upon  the  chemical  constitution  of 
these  shales  and  their  adaptability  for  plant  use  has  been 
a subject  of  preliminary  study  in  this  laboratory.  The 
results  obtained  were  in  some  of  their  phases  inconsistent 
and  it  is  the  purpose  of  this  investigation  to  determine 
the  reasons  for  the  results  of  certain  experiments  v/here 
variable  results  were  obtained. 


FT' 


3 


History. 

During  the  years  of  1916  and  1917  certain  Illinois 
shales  were  "being  studied  in  the  laboratory  of  applied 
chemistry  here  at  the  University  of  Illinois  with  reference 
to  the  amount  of  oil  they  would  produce  upon  destructive 
distillation.  Some  of  the  soils  proved  to  have  a quantity 
of  oil,  but  not  enough  to  make  them  of  value  from  this 
standpoint  alone.  They  were,  therefore,  examined  in  search 
of  other  values  and  certain  samples  were  found  to  contain 
considerable  amounts  of  potash. 

Shales  from  Dixon  County  and  Union  County,  Illinois 
were  examined,  and  it  was  found  that  the  potash  in  the 
Dixon  County  shales  was  mostly  in  the  feldspathic  form, 
while  that  from  Union  County  more  nearly  resemble  the 
glanconitic  form.  At  this  time  plant  cultures  were  con- 
ducted for  the  purpose  of  determining  which  form  of  potash 
was  the  most  beneficial  for  plant  growth,  and  it  was  found 
that  the  shale  from  Union  County  produced  a marked  improve- 
ment in  the  growths,  while  but  little  improvement  was  de- 
rived from  the  other* 

In  1916  because  of  the  potassium  famine  caused  by 
its  use  during  the  war  a search  for  an  American  substitute 
was  initiated.  This  led  to  a series  of  pot  cultures  using 
kainit,  leucite,  and  alunite  for  their  potassium  content. 
These  tests  spread  over  a period  of  three  years  and  vary- 
ing increases  in  yield  were  obtained.  At  a meeting  of  the 


Chemical  Research  Cluh  in  1919,  Prof.  S,  W,  Parr  sugges- 
ted that  the  Union  County  shale  of  Illinois  be  tested 
for  its  growth  producing  properties  along  with  the  kainit, 
alunite,  and  leucite.  The  results  obtsiined  ^?ith  the  shale 
v,rere  ver^’  favorable.  With  corn  fodder  the  yields  v^ere: 
kainit  93  grams  per  pot,  alunite  73  grains,  leucite  102, 
and  shale  165  grams. 

There  is  another  type  of  soil  in  Illinois,  a gray 
silt  loan,  which  responds  readily  to  the  application  of 
soluble  potassium  salts.  The  shale  was  used  with  this 
soil,  but  the  yields  v;ere  only  slightly  increased.  It 
was  thought  that  some  change  might  have  taken  place  in 
the  shale  between  applications.  However,  a fresh  supply 
of  shale  was  obtained  and  this  proved  to  be  no  better. 

The  agronomy  department  has  been  using  the  shale  in 
a series  of  cultures  viith  pure  sand,  so  that  the  only 
source  of  potassium  is  the  shale.  The  results  show  con- 
clusively that  the  shale  does  furnish  the  potassium  in 
a form  available  as  plant  food. 


5 


Experimental. 

In  an  endeavor  to  discover  a reason  for  the  vari- 
ation in  the  yields  produced  with  the  different  soils  it 
was  first  deemed  necessary  to  make  an  analysis  of  the 
tv/o  soils  used  for  various  plant  food  constituents,  on 
the  theory''  that  the  conversion  of  sulphur  into  a form 
available  for  plant  use  might  he  an  explanation  for  the 
increased  growths.  Such  an  analysis  might  then  indicate 
the  conditions  -which  were  lacking. 

Analyses  v/ere  made  of  the  soils  for  water  solu- 
ahle  and  acid  soluble  iron,  calcium  and  sulfate. 

Original  soils  used  in  previous  experiments. 


Organic 

Solvent 

Peat  Soil. 

6N-HCI 

- _ H2_0 

Gray  Silt 
6IT-HC1, 

Loam. 

H2O 

1 

o 

CO 

.40 

.22 

.21 

.19 

Ca 

. 50 

.12 

.97 

.05 

Fe 

1,11 

-- 

1.45 

-- 

Total  IT 

3.22 

.1.77 

This  soil  was  obtained 

from  a 

This  soil  was  obtained 

farm  eight 

miles  east 

of  Urbana, 

from  a farm  near  Momence. 

Illinois, 

Illinois. 

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Before  attempting  the  work  it  was  thought  that 
the  soil  could  be  obtained  for  the  purpose  of  conducting 
pot  cultures  in  an  effort  to  duplicate  the  results  first 
obtained  by  M,  M.  Austin.  The  Agromony  Department  of 
the  College  of  Agriculture  had  supposedly  some  of  the 
original  organic  peat  soil  at  their  disposal  and  the 
cultures  with  this  soil  was  started  when  desired.  This 
soil  was,  however f a new  supply  obtained  from  the  same 
place. 

It  was  necessary  to  secure  the  sandy  loam  from  a 
farm  near  Momence,  Illinois,  Heavy  rains  made  it  impos- 
sible to  remove  this  soil  and  caused  great  delay  in  start- 
ing this  set  of  cultures.  During  this  time  the  Agronomy 
Department  was  experimenting  with  shale  and  other  essen- 
tial plant  foods,  nitrogen  being  one  of  them.  The  results 
produced  were  evidence  that  the  shale  furnished  the  po- 
tassium, but  did  not  secure  vigorous  plants.  The  reason 
suggested  was  that  there  was  a deficiency  of  nitrogen. 

This  would  indicate  seemingly  by  the  analytical  values 
obtained  for  total  nitrogen,  nitrogen  was  therefore  ad- 
ded in  the  form  of  urea. 

As  far  as  possible  these  experiments  are  duplicates 
of  those  performed  by  M,  M.  Austin,  with  variations  in 
fertilizer  and  combinations  of  fertilizer  in  an  attempt 
to  show  by  the  difference  in  the  growth  of  the  plants  what 
was  lacking  in  the  soil  in  order  to  keep  the  shal^  from 
producing  the  desired  results. 


8 


Limestone  was  added  to  each  pot  at  the  rate  of 
sixty  grams  per  pot,  or  five  tons  per  acre.  This  v/as 
sufficient  to  neutralizie  the  acidity  of  the  soil  and 
also  any  acid  that  might  be  formed  by  the  conversion 
of  all  the  pryitic  sulfur  into  sulfuric  acid.  The 
amount  of  potassium  applied  to  the  pots  was  1.34  grams 
(which  is  equivalent  to  five  hundred  pounds  of  potas- 
sium sulfate  per  acre.)  Magnesium  chloride  was  applied 
at  the  rate  of  3.4  grams  per  pot.  Nitrogen  v/as  fur- 
nished as  urea  and  sulfate  as  calcium  sulfate,  both 
being  in  dilute  solution  and  applied  at  the  rate  of  .3 
of  a gram  per  pot  every  three  weeks.  Bacteria,  for 
the  conversion  of  the  sulfur  into  a for  available  for 
plant  nutrition,  were  added  to  the  pots  with  the  cal- 
cium sulfate.  This  bacterial  soil  was  obtained  from 
the  New  Jersey  Agricultural  Experiment  Station  at  New 
Brunswick,  New  Jersey, 

Conclusion 

The  first  set  of  plants  v/ere  started  with  the 
organic  peat  on  April  14,  1922  with  applications  of 
fertilizer  as  follows: 


No.  Of  pot. 

Treatment 

Plant . 

1,2 

Limestone 

Buckv/heat, 

3,4 

" , shale 

•• 

5 

tl 

1 

” , bacteria 

M 

II 

Rape 

3,9 

tl 

9 

II 

II 

10,11 

It 

9 

M tl 

9 

II 

12, 

II 

» 

" , "lAgCl^ 

II 

The  soil  is  exceedingly  rich,  and  as  shown  by 


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the  photographs,  produces  luxuriant  e:rowths  even  when 
untreated.  It  is  ordinarily  assumed  that  all  peat  soils 
are  deficient  in  potassium  and  the  pots  receiving  treatment 
will  best  show  the  effect  by  reference  to  the  ultimate 
weierht  of  the  crop.  The  photofcranhs  1 to  IS  herewith  do 
not  differentiate  sharnly  between  the  several  treatments, 
but  the  final  weiprhts  attained  are  more  characteristic. 


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The  follov/iner  table  which  was  obtained  June  28, 

1922,  thru  the  courtesy  of  Mr.  J.  J*  Anderson  of  the  Agronomy 
Department,  srives  the  green  weight  of  the  mature  plants 
resulting  from  the  different  treatments  for  this  first  series. 

Series  I 

Qreen  Weight  of  Matured  Plants  in  Or.?anic  Peat  Soil 


ITo.  of  Pot 

Treatment 

Plant 

Weip'ht  , 0rams 

1,  2 

Lime  stone 

Buckv/heat 

200  and  250 

3.  4 

Limestone  and  Shale 

TT 

220  and  230 

5 

Limestone,  Shale  and 
Bacteria 

270 

6,  7 

Limestone 

Pape 

400  and  470 

8,  9 

Limestone  and  Shale 

Tt 

450  and  470 

10,  11 

Limestone,  Shale  and 
Bacteria 

550  and  555 

12 

L_ 

[lim.estone.  Shale  and 
MarOlg 

560 

11 


The  eecond  series  of  plant  cultures  was  not 
started  until  May  1,  1922,  for  the  reasons  mentioned  before 
of  late  receipt  of  the  soil.  The  treatments  are  as 
follows : 

Series  II 

Sandy  Peat  from  Momence 


1 

No.  of  Pot 

Treatment 

PI  ant 

1 - 2 

Limestone 

Buchwheat 

1 

1 

1 i 

CQ 

Limestone,  shale 

Buc^^wheat 

5-6 

Limestone,  urea 

Buckwheat 

Y - 8 

Limestone,  shale,  urea 

Buckwheat 

9 -10 

Limestone,  shale,  urea 
bacteria,  Oa  SO4 

Buckwheat 

11-  12 

Limestone 

Rape 

13-  14 

Limestone,  Shale 

Rape 

15-  16 

Limestone,  shale,  urea 

Rape  i 

These  plants  have  not  at  this  date  (May  24)  had 
time  to  develop  sufficiently  to  furnish  any  information  with 
reference  to  yields.  This  soil  is  oris:inally  very  poor  and 
in  field  experience  produces  practically  nothins:  in  its 
normal  state. 

Photographic  illustrations  of  the  stac^es  are  driven 
in  lieu  of  harvesting  wei-'^hts  which  woull  only  be  available 
later  in  the  season. 


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An  evidence  of  differentiation  may  be  seen  in  these 
pots  even  at  the  early  stap:e  of  ??rowth  covered  by  these  photo- 
srraphs.  The  pots  Nos.  7 and  8 are  evidently  the  most 
advanced  in  the  buclOTheat  division  and  these  plants  received 
the  shale-urea  treatment  in  addition  to  the  limestone.  Here 
the  advantapre  is  clearly  due  to  the  shale-urea  combination. 

In  the  rape  series  an  evident  advantage  is  seen  in 
pots  Nos.  15  and  16  where  the  same  combination  of  shale  and 
urea  is  used  with  limestone.  Since  pots  11  and  12  have  lime- 
stone alone,  it  is  evident  that  this  soil  is  deficient  in 
both  potash  and  nitroyen.  It  is  unfortumate  that  this  series 
did  not  have  a bacteria  pot  and  that  all  were  not  carried  to 
maturity  and  weighed  as  in  Series  I. 

It  is  evident  that  peat  soils  vary  in  their  require- 
ment. In  the  rich  orpranic  peat  soil.  Series  I,  the  harvest 

weiprhts  indicate  an  advantapre  from  the  use  of  the  potash  shale, 
but  raarlcedly  better  with  the  shale  and  bacteria  combined. 

The  analysis  of  the  ororanic  peat  soil,  papre  6,  shows  an 
abundance  of  nitropren,  hence  no  urea  treatment  was  used.  In 
pot  No.  12  where  the  best  weip*ht  is  obtained  with  shale  and 
Ms^rOlg  the  su<?o:estion  is  obvious  that  the  bacteria  as  in  pots 
Nos.  10  and  11,  promote  the  availability  of  the  mavnesium 
which  is  present  (1.7  % MptO  ) in  the  shale. 

In  the  sandy  peat  there  is  an  evident  deficiency  in 
nitrop-en  as  well  as  in  potash.  Unfortunately  the  mavnesium 
factor  was  not  determined  by  a pot  experiment  and  no 
bacterial  inoculations  were  tried. 


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14 


The  work  is  su,?frestive  of  further  experiments  with 
other  baoterial  cultures  such  as  those  which  are  active  oxi- 
dizers of  sulfur  to  determine  the  effect  of  supplyinfy  especially 
sulfates  and  magnesia  as  well  as  potash  and  nitrogen. 


1 


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